Abstract

Silicon–lithium clusters are promising candidates for hydrogen storage due to their lightweight composition, high gravimetric capacities, and favorable non-covalent binding characteristics. In this study, we employ density functional theory (DFT), global optimization (AUTOMATON and Kick–MEP), and Born–Oppenheimer molecular dynamics (BOMD) simulations to evaluate the structural stability and hydrogen storage performance of key Li–Si systems. The exploration of their potential energy surface (PES) reveals that the true global minima of Li6Si6 and Li10Si10 differ markedly from those of the earlier Si–Li structures proposed as structural analogs of aromatic hydrocarbons such as benzene and naphthalene. Instead, these clusters adopt compact geometries composed of one or two Si4 (Td) units and a Si2 dimer, all stabilized by surrounding Li atoms. Motivated by the recurrence of the Si4–Td motif, we explore oligomers of Li4Si4, which can be viewed as electronically transmuted analogues of P4, confirming the additive H2 uptake across dimer, trimer, and tetramer assemblies. Within the series of Si–Li clusters evaluated, the Li12Si5 sandwich complex, featuring a ?-aromatic Si510? ring encapsulated by two Li65+ moieties, achieves the highest hydrogen capacity, adsorbing 34 H2 molecules with a gravimetric density of 23.45 wt%. Its enhanced performance arises from the high density of accessible Li+ adsorption sites and the electronic stabilization afforded by delocalized ?-bonding. BOMD simulations at 300 and 400 K confirm their dynamic stability and reversible storage behavior, while analysis of the interaction regions confirms that hydrogen adsorption proceeds via weak, dispersion-driven physisorption. These findings clarify the structure–property relationships in Si–Li clusters and provide a basis for designing modular, lightweight, and thermally stable hydrogen storage materials. © 2025 by the authors.